Adjustable chromophore compounds and materials incorporating such compounds

ABSTRACT

The present invention is directed to adjustable chromophore compounds and materials (e.g., ophthalmic lens materials) incorporating those compounds. The adjustable chromophore compounds include a chemical moiety that structurally changes upon exposure to predetermined electromagnetic radiation (e.g., two photon radiation) as well as lens materials, particularly intraocular lens materials that incorporate those compounds.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. Utility patent application Ser.No. 13/076,665 filed Mar. 31, 2011, now abandoned, which claims priorityunder 35 U.S.C. § 119 to U.S. Provisional Patent Application Ser. No.61/320,442, filed Apr. 2, 2010, the entire contents of which areincorporated herein by reference.

TECHNICAL FIELD OF THE INVENTION

The present invention is related to adjustable chromophore compounds andmaterials (e.g., ophthalmic lens materials) incorporating thosecompounds. More particularly, the present invention is related toadjustable chromophore compounds that includes a chemical moiety thatstructurally changes upon exposure to predetermined electromagneticradiation (e.g., two photon radiation) as well as lens materials (e.g.,intraocular lens materials) that incorporate those compounds.

BACKGROUND OF THE INVENTION

Chromophore compounds are molecules that absorb light and such lightabsorption is desirable for a wide range of products. They areparticularly important and useful in lenses of many different types. Asexamples, chromophores have been incorporated into lenses of sunglasses,lenses of spectacles, contact lenses and intraocular lenses (IOLs). Assuch, a significant amount of research has been performed investigatinga wide variety of compounds with light absorption characteristics.

It is typical for lenses such as those mentioned above to be formed ofpolymeric or glass matrices. Advantageously, the chromophores can bedispersed or distributed throughout portions or the entirety of thematrices and the concentrations of the chromophores can be substantiallyhomogeneous throughout the matrices or the concentrations can be variedin certain portions of the matrices.

For lenses, the amount and type (e.g., wavelength) of light absorptionprovided by any particular chromophore typically depends upon the amountand type (e.g., chemical structure) of chromophore used in a particularlens. This type and amount of chromophore is typically predetermined andprovides the lens with a particular predetermined light absorptionprofile. While this is generally acceptable for most lenses, there arecircumstances in which it may be desirable to change the absorptioncharacteristics of a chromophore after it has been incorporated into alens thereby changing the absorption profile provided by the lensitself.

As one example, individuals having intraocular lens (IOLs) may beparticularly desirous of having the ability to change the absorptionprofile provided by the chromophores in their lenses. Individuals thatwill be exposed to greater amounts of sunlight due to geographicalchanges, activity (e.g., employment) changes or other changes in theirlives may desire a change in the absorption profile of their IOLs.Individuals that have or develop sensitivity to particular wavelengthsof light may desire a change in the absorption profile. It would also bedesirable to be able to tune the absorption profile of an IOL for allindividuals receiving IOLs.

It is also the case that some chromophore compounds tend to degrade overtime due to absorption of light. In this circumstance, it would bedesirable to be able to adjust the absorption profile of the lens tocompensate for the degradation of the chromophores.

In view of the above, it would be particularly desirable to provide achromophore with adjustable light absorption characteristics. It wouldalso be particularly desirable to provide such chromophore compoundwithin a product (e.g., lens) wherein the absorption profile of the lenscould be adjusted after incorporation of the chromophore compound intothe lens.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to an adjustablechromophore comprising a compound of the formula:B—X;

wherein:

-   -   i) B is a base chromophore compound; and    -   ii) X is an adjustable chemical moiety that forms a remaining        chemical moiety (C) upon exposure to predetermined        electromagnetic radiation thereby forming the compound:        B—C;    -   iii) the compound B—C provided greater light absorption than the        compound B—X; and    -   iv) the remaining chemical moiety (C) includes a conjugated        double bond.

The present invention is also directed to a lens comprising a polymericmaterial and the adjustable chromophore compound, as described herein,distributed within the polymeric material. The material that includesthe chromophore compound can typically absorb light at progressivelygreater wavelengths as greater amounts of the compound B—C are formedfrom the adjustable compound B—X.

The present invention is also directed to a method of adjusting a lensin vivo or in vitro. The method includes directing predeterminedelectromagnetic radiation as described herein at the above describedlens to form the compound B—C either prior to or after implantation ofthe lens in the eye.

The present invention is also directed to an adjustable chromophoresystem, comprising a compound of the formula:B—X or B—C

as part of the reactive system:B—X⇄B—C

wherein:

-   -   i) B is a base chromophore compound; and    -   ii) X is an adjustable chemical moiety that forms remaining        chemical moiety (C) upon exposure to first predetermined        electromagnetic radiation thereby forming the compound B—C:    -   iii) the compound B—C provides greater light absorption than the        compound B—X; and    -   iv) the remaining chemical moiety (C) includes a conjugated        double bond; and    -   v) optionally, the compound B—C forms the compound B—X upon        exposure to second predetermined electromagnetic radiation        either with or without the aid of a separable group (S).

The base chromophore of the lens, the system or the adjustablechromophore is preferably selected from the group consisting ofbenzotriazoles, benzophenones, azo dyes and cinnamate esters. Thecompound B—C typically absorbs a significant amount of UV light, bluelight or both. Moreover, the adjustable chemical moiety X is apreferably a cyclic moiety such as dicyclopentadiene.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B are respectively, a top and sectional view of a contactlens in accordance with an aspect of the present invention.

FIGS. 2A and 2B are respectively, a top and sectional view of anintraocular lens in accordance with an aspect of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is predicated upon the provision of an adjustablechromophore compound and/or system. The absorption characteristics(e.g., absorption profile) of the chromophore compound will beadjustable upon exposure to predetermined electromagnetic radiation. Thepresent invention is also predicated upon the provision of products,particularly lenses (e.g., lens of sunglasses, lenses of spectacles,IOLs, contact lenses or the like), that incorporate the adjustablechromophore compounds and/or system of the present invention such thatthe absorption profile of those products can be adjusted.

The adjustable chromophore compound will typically have the followingchemical structure:B—X

-   wherein:-   B is a base chromophore compound; and-   X is an adjustable chemical moiety that forms a separable group (S)    and a remaining chemical moiety (C) upon exposure to the    predetermined electromagnetic radiation thereby forming the    compound:    B—C;    Typically, the remaining chemical moiety (C) includes a conjugated    double bond. Advantageously, such conjugated double bond provides    significant adjustment to the absorption characteristics (e.g.,    absorption profile) of resultant chromophore compound B—C relative    to the adjustable chromophore compound B—X.

A great number of chromophores are known and may be used as the basechromophore compound (B). In a preferred embodiment, however, the basechromophore compound is selected from the group consisting ofbenzotriazoles, benzophenones, azo dyes and cinnamate esters. In ahighly preferred embodiment the base chromophore compound is abenzotriazole or benzophenone, but is most typically a benzotriazole.Examples of benzotriazoles suitable as the base chromophore compound aredisclosed in U.S. Pat. Nos. 4,528,311 and 7,396,942; and U.S. PatentApplication Nos. 2010/0012889 and 2008/0090937, all of which are fullyincorporated herein in their entirety by reference for all purposes.Other examples of potentially suitable base chromophore compounds aredisclosed in US Patent Application Publication Nos. 2007/0077214;2008/0242818; and 2002/0025401, all of which are fully incorporatedherein in their entirety by reference for all purposes.

The adjustable chemical moiety (X) can be any moiety that can beseparated into the remaining chemical moiety (C) and the separable group(S) upon exposure to the predetermined electromagnetic radiation.Typically, the chemical moiety (X) is cyclical and, upon separation intothe chemical moiety (C) and the separable group (S), provides thechemical moiety (C) with a conjugated double bond. Schematically, such areaction would be as follows:X→C+SOr

Examples of moieties suitable for use as the adjustable chemical moiety(X) include, without limitation, dicyclopentadiene, dicyclohexadiene,cyclobutane, cyclohexene or the like. It shall be understood that thestructures of the chemical moiety (C) and the separable group (S) willbe dictated by the structure of the chemical moiety (X) and, in certaincircumstance, vice-versa. It will also be understood that the separablegroup (S) could be bound within a polymer matrix of the polymer, couldbe entangled in the polymer matrix, but may not be either.

The adjustable chromophore system of the present invention includes anadjustable chromophore compound of the present invention and thatadjustable chromophore compound can be adjusted to the resultantchromophore compound B—C but that adjustment is then reversible suchthat the resultant chromophore compound B—C can be adjusted back to theadjustable compound B—X. Thus, the adjustable chromophore systemincludes a compound of the formula:B—X, B—C or bothas part of the reactive system:B—X⇄B—C+Swherein:

-   B is the base chromophore compound; and-   X is the adjustable chemical moiety that forms separable group (S)    and remaining chemical moiety (C) upon exposure to a first    predetermined electromagnetic radiation thereby forming the compound    B—C where the remaining chemical moiety (C) includes a conjugated    double bond. It is then possible that the separation of the    adjustable chemical moiety (X) into the remaining chemical    moiety (C) and the separable group (S) may be reversible upon    exposure to a different predetermined electromagnetic radiation to    form the compound B—X. In such instance, the system will be able to    add to the level of absorption provided by the system or subtract    from the amount of absorption provided by the system depending upon    the electromagnetic radiation provided thereto.

The chromophore compound B—X and chromophore compound B—C can include anelectron donating chemical moiety (D), an electron withdrawing chemicalmoiety (W) or both and those moieties will typically remain with thechromophore compound B—C after the adjustable moiety (X) is separatedinto the remaining moiety (C) and the separable group (S). The donatingmoiety (D) and the withdrawing moiety (W) can be part of the basechromophore compound (B), the adjustable chemical moiety (X) and/or theremaining chemical moiety (C). Typically, if the donating moiety (D) ispart of the base chromophore compound (B), then the withdrawing moiety(W) is part of the adjusting chemical moiety (X) and the remainingchemical moiety (C) and vice versa.

A variety of suitable electron withdrawing moieties (W) will be evidentto the skilled artisan. Examples of suitable electron withdrawingmoieties (W) include cyano groups, carbonyls, esters, amides, sulfonyls,halogens, combinations thereof or the like. In a preferred embodiment,the withdrawing moiety (W) is a halogen (e.g., a halogen itself or ahalogen inclusive group) such as fluorine (F), chlorine (Cl), carbontrifluoride (CF₃) or the like. A variety of suitable electron donatingmoieties (D) will also be evident to the skilled artisan. Examples ofsuitable donating moieties (D) include, without limitation, alkyl groupssuch as methyl groups and ethyl groups, alkoxy groups, amino groups orthe like.

Advantageously, the donating moiety (D), the withdrawing moiety (W) orboth can aid in polarizing the chromophore compound B—C. Suchpolarization can aid the ability of the chromophore compound B—C inabsorbing light, particularly additional wavelengths of light (e.g.,higher or longer wavelengths of light). Moreover, such polarization canbe significantly blocked by the adjustable chemical moiety (X) such thatthe light absorption ability of the chromophore compound B—X issignificantly reduced (e.g., can be less than 80% or even 60%) relativeto the light absorbing ability of the chromophore compound B—C.

The adjustable moiety (X) can additionally or alternatively include amobilization inhibiting moiety (Z) and that moiety will typically remainwith the separable group (S) after the adjustable moiety (X) isseparated into the remaining moiety (C) and the separable group (S).Such a mobilization inhibiting moiety (Z) is particularly useful forsituation where the chromophore compound B—X is incorporated into amatrix (e.g., a polymer or glass matrix) for maintaining the separablegroup (S) in the matrix after the adjustable moiety (X) is separatedinto the remaining moiety (C) and the separable group (S). Typically,the mobilization inhibiting moiety is capable of entangling in thematrix. Preferably, the mobilization inhibiting moiety (Z) is orincludes a substituted or unsubstituted alkyl group (e.g., an alkanechain) with a carbon chain or carbon based group having a carbon atomsin the range of C₄-C₂₀, more typically C₅-C₁₂ and even possibly C₆-C₁₀.

The chromophore compounds and/or system of the present invention can beincorporated into a variety of different products. Most significantly,however, they can be incorporated into lenses of products such assunglasses or spectacles or into contact lenses or IOLs. The chromophorecompounds and system can be incorporated into these lenses whether theyare formed of glass or polymeric material or a combination thereof.Typically, these materials, whether thermoset or thermoplastic, willform a matrix and the compounds and/or system can be distributed ordispersed throughout the entirety or a portion of the matrix.

The chromophore compounds and/or system of the present invention can beincorporated into matrices of materials commonly used to form sunglassesor spectacles. Such materials can include glass or polymeric materialssuch as polystyrene, polycarbonate, acrylics, combinations thereof orthe like.

The chromophore compounds and/or system of the present invention can beincorporated into contact lenses, IOLs or both. Contact lenses and IOLstypically includes matrices formed of acrylate based materials (i.e.,materials that are formed of at least 20%, at least 50% or more acrylatemonomers such as phenylethyl methacrylate and hydoxyethyl methacrylate),silicone materials or the like. The skilled artisan will understand thatchromophore compounds generally have been included in these types oflenses and/or matrices and the chromophore compounds of the presentinvention can be incorporated in a similar manner.

The adjustment of the chromophore compound of the present invention canoccur prior to incorporation into a product or material matrix, butpreferably occurs thereafter. As suggested, the adjustment is caused byexposure of the chromophore compounds, particularly the adjustablemoiety (X) to predetermined electromagnetic radiation. The particularlyradiation employed to form the adjustable moiety (X) into the remainingmoiety (C) and the separable group (S), or vice versa, will depend uponthe chemical structure of those groups and/or moieties. Thatelectromagnetic radiation can be from the visible part of theelectromagnetic spectrum or from the non-visible part of theelectromagnetic spectrum. In preferred embodiments, the predeterminedelectromagnetic radiation is provided as relatively intense ultraviolet(UV) radiation. In another preferred embodiment, the predeterminedradiation is provided as infrared (IR) radiation. In one particularlypreferred embodiment, the electromagnetic radiation is provided astwo-photon radiation that is typically from the visible portion of theelectromagnetic spectrum. Advantageously, the two photon radiation canbe provided as light from the visible portion of the electromagneticspectrum.

The predetermined electromagnetic radiation is provided from a lightsource such as a laser or other light or energy source that can directthe radiation at the chromophores or at the materials into which thechromophores have been incorporated. Most commonly, the predeterminedelectromagnetic radiation will have a wavelength and/or frequencyconfigured to result in the following reaction scheme:B—X→B—C+Swherein the adjustable chromophore compound B—X is exposed to thepredetermined radiation to produce the chromophore compound B—C and theseparable group (S). Moreover, within the system of the presentinvention, a second predetermined electromagnetic radiation will have awavelength and/or frequency configured to cause the reversal of thatreaction.

It will also be understood, particularly with reference to Example 4below, that the chromophore compound B—X can be converted directly toB—C without the formation of a separable group. This scheme can occur,as it does in Example 4, according to the following reaction scheme:B—X—B⇄B—C+B—CAlternatively, the chemical entity which would normally be the separablegroup (S) might be or become chemically bonded with and be part of thebase chromophore such that system of the present invention could occuraccording to the following scheme:B—X⇄B—C

In this invention, the chromophore compound B—C will typically provide asignificantly greater amount of light absorption than the adjustablechromophore compound B—X. Moreover, it is possible and often desirablethat, as more of the chromophore compound B—C is formed, greater amountsof light at greater wavelengths are absorbed. In this scenario, theabsorption cutoff of the material that include the chromophore compoundB—C will move toward progressively higher wavelengths as more and moreof the chromophore compound B—C is formed.

As a quantification of this change in absorption, it is desirable for amaterial including compound B—X to absorb at least 80% of light at afirst wavelength and less than 20% of light at a second wavelength whenless than 25% of a starting amount or concentration of compound B—X hasbeen converted to compound B—C and separable group (S), but for thematerial to absorb at least 80% of light at the first wavelength and atleast 80% of light at the second wavelength after at least 75% of thestarting amount or concentration of the compound B—X has been convertedto compound B—C. In such a situation, the first wavelength is at least 5nanometers, more preferably at least 10 nanometers and even possibly atleast 15 nanometers less than the second wavelength.

As suggested above, it is also contemplated that the chromophorecompound B—C and separable group (S) can be exposed to predeterminedradiation to produce adjustable chromophore compound B—X. As aquantification of this absorption, it is desirable for a materialincluding compound B—C and separable group (S) to absorb at least 80% oflight at a first wavelength and light at a second wavelength when lessthan 25% of a starting amount or concentration of compound B—C andseparable group (S) has been converted to compound B—X but for thematerial to absorb at least 80% of light at the first wavelength butless than 20% of light at the second wavelength after at least 75% ofthe starting amount or concentration the compound B—C and the separablegroup (S) has been converted to compound B—X. In such a situation, thefirst wavelength is at least 5 nanometers, more preferably at least 10nanometers and even possibly at least 15 nanometers less than the secondwavelength.

For ophthalmic lenses, particularly IOLs and/or contact lenses, thechromophores B—X and/or B—C are typically designed to providesubstantial absorption (e.g., at least 50% and even at least 80%) oflight at wavelengths in the UV range up to and even into portions of theblue light range. As such, the first and second wavelengths, asdiscussed above, will typically be in the UV to blue portions of theelectromagnetic spectrum. Thus, in preferred embodiments, the first andsecond wavelengths are both preferably in the range of 300 to 500, morepreferably 380 to 470 and even more preferably 390 to 440 nanometers.

The skilled artisan will understand that the IOLs and contact lensesthat will receive the chromophore compounds of the present inventionwill be sized and shaped suitably for application to the eye. Withreference to FIGS. 1A and 1B, a contact lens 10 will typically have alargest outer perimeter (e.g., largest peripheral circumference) 12 ofat least 2, more typically at least 3 and even more typically at least 4centimeters. The largest perimeter 12 will also typically be less than10, more typically less than 6 and even more typically less than 5.5centimeters. The contact lens will also typically include a concavesurface 14 opposing a convex surface 16. With reference to FIGS. 2A and2B, an IOL 20 will typically have a largest outer perimeter (e.g.,largest peripheral circumference) 22 of at least 1.5, more typically atleast 2.0 and even more typically at least 3.2 centimeters. The largestperimeter 22 will also typically be less than 7, more typically lessthan 5 and even more typically less than 4.5 centimeters. Aphakic IOLswill also typically include a first convex surface 24 opposing a secondconvex surface 26 whereas phakic IOLs may have convex surfaces like theaphakic IOLs or convex/concave surfaces like the contact lenses.

While these absorption adjustments can occur in vitro, it is alsocontemplated that they may occur in vivo. For example, and withoutlimitation, both contact lenses and IOLs may be adjusted afterapplication or implantation of those lenses to a mammalian eye,particularly a human eye. This is particularly the case where visiblelight (e.g., two photon light) is used to adjust the absorptioncharacteristics. A discussion of techniques of using two photon light toadjust refractive index of implanted IOLs is provided in US PatentPublication No. 2009/0157178, which is fully incorporated herein byreference for all purposes. Advantageously, such techniques might alsobe used to adjust the chromophores of the present invention.

As a further advantage of the present invention, the predeterminedradiation can be directed at particular portions of the lens to enhancelight absorption in particular pre-selected regions of the lens whileother regions of the lens will exhibit less absorption. For an IOL, forexample, it might be desirable to enhance the light absorption of anucleus portion of the IOL while leaving the peripheral portion of theIOL to exhibit less light absorption. Such an IOL would then exhibit thegreater light absorption when light is bright and the pupil of the eyeis small and would exhibit less absorption when there is less light andthe pupil of the eye is larger. In such an embodiment, the nucleusregion will typically have a concentration of the chromophore compoundB—C that is greater than 120% and more typically greater than 150% ofthe concentration at a peripheral region of the lens. Such nucleusregions and such peripheral regions will both be at least 10% of theoverall volume of the IOL excluding any haptics.

EXAMPLES Example 1

Example 1 above illustrates one exemplary embodiment of the invention.As can be seen, a chromophore compound B—X includes a benzotriazole basechromophore (B) and an adjustable moiety (X), which is adicyclopentadiene. The adjustable moiety (X) includes a mobilizationinhibiting group (Z), which is preferably an alkane chain, and anelectron donating moiety (D), which is preferably an alkoxy group. Thebase chromophore compound (B) includes an electron withdrawing group(W), which is preferably one of the halogen or halogenated groupsdiscussed above. As can be seen, upon exposure to predeterminedradiation, the chromophore compound B—X becomes the chromophore compoundB—C and separable group (S) with the chromophore compound B—C having aconjugated double bond and the electron donating group (D) as well asthe remaining group (C). The base chromophore (B) then includes theelectron withdrawing group (W). Further, the separable group (S)includes the mobilization inhibiting group (Z).

Example 2

Example 2 above illustrates another exemplary embodiment of theinvention. As can be seen, a chromophore compound B—X includes abenzotriazole base chromophore (B) and an adjustable moiety (X), whichis a dicyclopentadiene. The adjustable moiety (X) includes amobilization inhibiting group (Z), which is preferably an alkane chain,and an electron withdrawing moiety (W), which is preferably a halogengroup. The base chromophore compound (B) includes an electron donatinggroup (D), which is preferably an alkoxy group. As can be seen, uponexposure to predetermined radiation, the chromophore compound B—Xbecomes the chromophore compound B—C and separable group (S) with thechromophore compound B—C having a conjugated double bond and theelectron withdrawing group (W) as well as the remaining group (C). Thebase chromophore (B) then includes the electron donating group (D).Further, the separable group (S) includes the mobilization inhibitinggroup (Z).

Example 3

Example 3 above illustrates another exemplary embodiment of theinvention. As can be seen, a chromophore compound B—X includes abenzotriazole base chromophore (B) and an adjustable moiety (X), whichis a dicyclopentadiene. In this example, a cyclic moiety of the basechromophore (B) and the dicyclopentadiene share a common bond. Theadjustable moiety (X) includes a mobilization inhibiting group (Z),which is preferably an alkane chain. Further, the w base chromophore (B)includes an electron withdrawing moiety (W), which is preferably ahalogen group and an electron donating group (D), which preferablyincludes an alkoxy group. As can be seen, upon exposure to predeterminedradiation, the chromophore compound B—X become the chromophore compoundB—C and separable group (S) with the chromophore compound B—C having ais conjugated double bond as the remaining group (C) and the electronwithdrawing group (W). The base chromophore (B) also includes theelectron donating group (D). Further, the separable group (S) includesthe mobilization inhibiting group (Z),

Example 4

Example 4 above illustrates another exemplary embodiment of the systemof the invention. As can be seen, a pair of base chromophore compounds(B), which are both benzotriazoles are both bonded to a singleadjustable moiety (X), which is a cyclobutane, to form the compoundB—X—B. Each of the base chromophore compounds (B) include both anelectron withdrawing moiety (W), which is preferably a halogen group andan electron donating group (D), which preferably includes an alkoxygroup. As can be seen, upon exposure to predetermined radiation, thechromophore compound B—X—B becomes two separate chromophore compoundsB—C with each of the chromophore compounds B—C having a remaining group(C) with a conjugated double bond. Moreover, upon exposure to a secondpredetermined radiation, the chromophore compounds B—C can be reacted tobecome the single chromophore compound B—X—B.

Applicants specifically incorporate the entire contents of all citedreferences in this disclosure. Further, when an amount, concentration,or other value or parameter is given as either a range, preferred range,or a list of upper preferable values and lower preferable values, thisis to be understood as specifically disclosing all ranges formed fromany pair of any upper range limit or preferred value and any lower rangelimit or preferred value, regardless of whether ranges are separatelydisclosed. Where a range of numerical values is recited herein, unlessotherwise stated, the range is intended to include the endpointsthereof, and all integers and fractions within the range. It is notintended that the scope of the invention be limited to the specificvalues recited when defining a range.

Other embodiments of the present invention will be apparent to thoseskilled in the art from consideration of the present specification andpractice of the present invention disclosed herein. It is intended thatthe present specification and examples be considered as exemplary onlywith a true scope and spirit of the invention being indicated by thefollowing claims and equivalents thereof.

I claim:
 1. A method of adjusting the light absorption characteristicsof an intraocular lens, the method comprising: implanting into a patienta lens having a compound selected from the group consisting of:

wherein W is an electron withdrawing moiety; D is an electron donatingmoiety; and Z is a mobilization inhibiting moiety; and exposing the lensto electromagnetic radiation sufficient to adjust the amount of UVlight, blue light, or both that the lens absorbs.
 2. The method of claim1 wherein W is selected from the group consisting of Cl, F, and CF₃. 3.The method of claim 1 wherein D is selected from the group consisting ofalkyl, alkoxy, and amino groups.
 4. The method of claim 1 wherein Z isselected from the group consisting of unsubstituted or substitutedC₄-C₂₀ alkyl.